JP2009522730A - Cationic composition of conducting polymer doped with perfluorinated acid polymer - Google Patents

Abstract

A conductive polymer composition is provided. The composition contains a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups. The first portion of the acidic anionic group forms a complex with the conductive polymer. The second portion of the acidic anionic group is in the form of a salt with a cation that may be an inorganic cation, an organic cation, and combinations thereof. The concentration of this cation is in the range of 5 × 10 ^{−5 to} 0.2 moles of cation per gram of solid content, and this solid content is mainly comprised of the conductive polymer and the fully fluorinated acid polymer. Total.

Description

  The present invention relates generally to conductive polymer compositions and their use in organic electronic devices.

(Cross-reference of related applications)
This application claims priority to US Provisional Patent Application No. 60 / 754,338, filed December 28, 2005, the entire contents of which are incorporated herein by reference.

  Organic electronic devices are defined as one of the categories of products that include an active layer. Such devices convert electrical energy into radiation, detect signals via electronic processes, convert radiation into electrical energy, or include one or more organic semiconductor layers. .

An organic light emitting diode (OLED) is an organic electronic device that includes an organic layer capable of electroluminescence. The OLED can have the following configuration:
Anode / buffer layer / EL material / cathode Generally, the anode is any material that is transparent and capable of injecting holes into the EL material, such as, for example, indium / tin oxide (ITO). In some cases, the anode is supported on a glass or plastic substrate. EL materials include fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof. Typically, the cathode is any material (such as Ca or Ba) that has the ability to inject electrons into the EL material. The buffer layer is typically a conductive polymer and facilitates the injection of holes from the anode into the EL material layer. The buffer layer can also have other properties that promote device performance.

US Pat. No. 5,463,005 US Patent Application Publication No. 2005-0184287 International Publication No. 2005/052027 Pamphlet US Pat. No. 6,670,645 International Publication No. 03/063555 pamphlet International Publication No. 2004/016710 Pamphlet International Publication No. 03/008424 Pamphlet International Publication No. 03/091688 Pamphlet WO03 / 040257 pamphlet US Pat. No. 6,303,238 International Publication No. 00/70655 Pamphlet International Publication No. 01/41512 Pamphlet US Pat. No. 6,150,426 US Patent Application Publication No. 2004-02542970 US Patent Application Publication No. 2005-0205860 Macromolecules, 34, 5746-5747 Mitsugu (2001) Macromolecules, 35, 7281-7286 (2002) A. Fairing et al. Fluorine Chemistry 2000, 105, 129-135 A. Feiring et al., Macromolecules 2000, 33, 9262-9271 D. D. Demarteau, J.M. Fluorine Chem. 1995, Volume 72, 203-208 Mitsugu A. J. et al. Appleby et al. Electrochem. Soc. 1993, 140 (1), 109-111 "Flexible light-emitting diode made from solid conducting polymer", Nature 357, 477-479 (June 11, 1992) Y. Kirk Osmer Encyclopedia of Chemical Technology, 4th edition (Fourth Edition), Vol. 18, pages 837-860, 1996.

  There is a continuing need for cushioning materials with improved properties.

A conductive polymer composition comprising a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups, wherein the first part of the acidic anionic groups forms a complex with the conductive polymer, and is acidic The second portion of the anionic group is in the form of a salt with a cation selected from inorganic cations, organic cations, and combinations thereof, and the cation concentration is 5 × per gram of solids. Provided is a conductive polymer composition in the range of 10 ^{−5 to} 0.2 moles of cation, wherein the solid content consists essentially of the sum of the conductive polymer and the fully fluorinated acid polymer.

In another embodiment, an aqueous dispersion of a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups, wherein the first portion of acidic anionic groups is a composite with the conductive polymer Wherein the second portion of the acidic anionic group is in the form of a salt with a cation selected from an inorganic cation, an organic cation, and combinations thereof, wherein the concentration of the cation is Providing an aqueous dispersion in the range of 5 × 10 ^{−5 to} 0.2 moles of cation per gram, wherein the solid content consists essentially of the sum of the conductive polymer and the fully fluorinated acid polymer To do.

  In another embodiment, an electronic device is provided that includes at least one layer comprising the novel conductive polymer composition of the present invention.

  The foregoing summary and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, which is defined by the appended claims.

  In order to facilitate an understanding of the concepts presented herein, embodiments are described in the accompanying drawings.

  As will be appreciated by those skilled in the art, the objects in the drawings are shown for simplicity and clarity and are not necessarily drawn to scale. For example, in order to facilitate understanding of the embodiments, the dimensions of some objects in the drawings may be exaggerated more than other objects.

  Many aspects and embodiments have been described above and are merely exemplary and not limiting. After reading this specification, skilled artisans will appreciate that other aspects and embodiments are possible without departing from the scope of the invention.

  Other features and advantages of any one or more embodiments of the invention will be apparent from the following detailed description and from the claims. This detailed description first deals with definitions and explanations of terms, followed by the preparation of conducting polymers, perfluorinated acid polymers, cations, doped conducting polymer compositions, substitution of acidic protons with cations. , Electronic devices, and finally working examples.

(1. Definitions and explanations of terms used in the specification and claims)
Before addressing details of the embodiments described below, some terms are defined or explained.

As used herein, the term “conductor” and variations thereof refer to a layer material, member, or material having electrical properties such that current flows through the layer material, member, or structure without a substantial drop in potential. Or intended to mean structure. This term is intended to include semiconductors. In one embodiment, the conductor forms a layer having a conductivity of at least 10 ⁻⁷ S / cm.

  The term “conductive material” means a material that can be inherently or essentially conductive without the addition of carbon black or conductive metal particles.

  The term “buffer layer” or “buffer material” is intended to mean a conductive or semiconductor material, including but not limited to planarization of the underlying layer, charge transport and / or charge injection. One or more functions may be included in the organic electronic device, such as properties, trapping impurities such as oxygen or metal ions, and other features that facilitate or improve the performance of the organic electronic device. The buffer material may be a polymer, oligomer, or molecule, and may be in the form of a solution, dispersion, suspension, emulsion, colloidal mixture, or other composition.

  When referring to a layer, material, member, or structure, “hole transport” means that such layer, material, member, or structure is such that the layer, material, member, or structure is relatively efficient and with low charge loss. It is intended to mean that it facilitates the movement of positive charges through the thickness of a member, or structure. The emissive layer may have some hole transport properties, but as used herein, the term “hole transport layer” does not include the emissive layer.

  The term “polymer” is intended to mean a material having at least one repeating monomer unit. The term includes homopolymers having only one type or species of monomer units, and copolymers having two or more different monomer units, such as copolymers formed from monomer units of different species.

  The term “perfluorinated acid polymer” means a polymer having acidic groups in which all of the reactive hydrogen bonded to the carbon is replaced with fluorine.

  The term “acidic group” means a group that can be ionized to donate a hydrogen ion to a Bronsted base to form a salt.

  The term “acidic anionic group” means an anionic group that remains after hydrogen ions are removed from the acidic group.

  The compositions of the present invention can include one or more different conductive polymers and one or more different perfluorinated acid polymers.

  The term “doped” when referring to a conductive polymer is intended to mean that the conductive polymer has a polymer counterion to balance the charge on the conductive polymer.

  The term “doped conductive polymer” is intended to mean a conductive polymer and a polymer counterion associated therewith.

  As used herein, the terms “comprising”, “comprising”, “comprising”, “comprising”, “having”, “having”, or any other variation thereof, Intended to deal with non-exclusive inclusions. For example, a process, method, article, or apparatus that includes a set of elements is not necessarily limited to those elements, and may be unspecified or unique with respect to such processes, methods, articles, or apparatuses. There can be no other elements. Further, unless stated to the contrary, “or” means an inclusive “or” and not an exclusive “or”. For example, condition A or B is satisfied when A is true (or present) B is false (or does not exist) and A is false (or does not exist) B is true (or Present) and both A and B are true (or present).

  “A” or “an” is also used to describe elements and components of the present invention. This is merely for convenience and is done to provide a general sense of the invention. This description should be read to include one or at least one and the singular also includes the plural unless it is obvious that it is meant otherwise.

Group numbers corresponding to columns in the Periodic Table of Elements are “new notation” (2000-2001), which can be found in the CRC Handbook of Chemistry and Physics, 81 ^st Edition (2000-2001). New Notation) rules are used.

  Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference in their entirety, unless a particular part is cited. In case of conflict, the present specification, including definitions, will control. In addition, the materials, methods, and examples are illustrative only and not intended to be limiting.

  Many details regarding specific materials, processing acts, and circuitry to the extent not described herein are conventional, including organic light emitting diode displays, illumination sources, photodetectors, photovoltaic cells, and It can be found in textbooks and other information sources in the technical field of semiconductor elements.

(2. Conductive polymer)
In one embodiment, the conductive polymer of the present invention forms a film having a conductivity of at least 10 -7 ^{S / cm.} The monomer from which the conductive polymer is formed is called the “precursor monomer”. The copolymer has two or more precursor monomers.

  In one embodiment, the conductive polymers of the present invention are generated from at least one precursor monomer selected from thiophenes, selenophenes, tellurophenes, pyrroles, anilines, and polycyclic aromatics. The polymers produced from these monomers are referred to herein as polythiophene, poly (selenophene), poly (tellurophene), polypyrrole, polyaniline, and polycyclic aromatic polymers, respectively. The term “polycyclic aromatic” means a compound having two or more aromatic rings. These rings may be linked by one or more bonds or may be fused together. The term “aromatic ring” is intended to include heterocyclic aromatic rings. “Polycyclic heteroaromatic” compounds have at least one heterocyclic aromatic ring. In one embodiment, the polycyclic aromatic polymer is poly (thienothiophene).

  In one embodiment, the monomer contemplated for use to form the conductive polymer in the novel composition of the present invention is represented by the following Formula I:

In the formula:
Q is selected from the group consisting of S, Se, and Te;
R ¹ is independently selected to be the same or different for each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, Amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane , Siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate And both R ¹ groups together form an alkylene chain or alkenylene chain, thereby forming a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring A formula ring can be completed, and the ring can optionally contain one or more divalent nitrogen, selenium, tellurium, sulfur, or oxygen atoms.

  As used herein, the term “alkyl” refers to a group derived from an aliphatic hydrocarbon and refers to linear, branched, and cyclic groups that may be unsubstituted or substituted. Contains. The term “heteroalkyl” is intended to mean an alkyl group in which one or more carbon atoms in the alkyl group is replaced with another atom such as nitrogen, oxygen, sulfur, and the like. The term “alkylene” refers to an alkyl group having two points of attachment.

  As used herein, the term “alkenyl” means a group derived from an aliphatic hydrocarbon having at least one carbon-carbon double bond, whether unsubstituted or substituted. Contains certain linear, branched, and cyclic groups. The term “heteroalkenyl” is intended to mean an alkenyl group in which one or more carbon atoms in the alkenyl group is replaced with another atom, such as nitrogen, oxygen, sulfur, and the like. The term “alkenylene” refers to an alkenyl group having two points of attachment.

As used herein, the following terms for substituents refer to the formulas shown below:
“Alcohol” —R ³ —OH
“Amido” —R ³ —C (O) N (R ⁶ ) R ⁶
“Amidosulfonate” —R ³ —C (O) N (R ⁶ ) R ⁴ —SO ₃ Z
“Benzyl” —CH ₂ —C ₆ H ₅
“Carboxylate” —R ³ —C (O) OZ or —R ³ —O—C (O) —Z
“Ether” —R ³ — (O—R ⁵ ) _p —O—R ⁵
“Ether carboxylate” —R ³ —O—R ⁴ —C (O) OZ or —R ³ —O—R ⁴ —O—C (O) —Z
“Ether sulfonate” —R ³ —O—R ⁴ —SO ₃ Z
“Estersulfonate” —R ³ —O—C (O) —R ⁴ —SO ₃ Z
“Sulfonimide” —R ³ —SO ₂ —NH—SO ₂ —R ⁵
“Urethane” —R ³ —O—C (O) —N (R ⁶ ) ₂
Where all “R” groups are the same or different each time they appear:
R ³ is a single bond or an alkylene group, R ⁴ is an alkylene group, R ⁵ is an alkyl group, R ⁶ is hydrogen or an alkyl group, p is 0 or an integer of 1 to 20, and Z is H, an alkali group It is a metal, an alkaline earth metal, N (R ⁵ ) ₄ , or R ⁵ .
Any of the above groups may be further substituted or unsubstituted, and any group may have one or more hydrogens replaced with F, such as a perfluorinated group. In one embodiment, the alkyl and alkylene groups have 1 to 20 carbon atoms.

In one embodiment, in the monomer, both R ¹ together form —O— (CHY) _m —O—, wherein m is 2 or 3, and Y is And selected from hydrogen, halogen, alkyl, alcohol, amide sulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane, and these Y groups are moieties It may be target or fully fluorinated. In one embodiment, all Y are hydrogen. In one embodiment, the polymer is poly (3,4-ethylenedioxythiophene). In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent in which at least one hydrogen is replaced with F. In one embodiment, at least one Y group is perfluorinated.

  In one embodiment, the monomer has the formula I (a):

In the formula:
Q is selected from the group consisting of S, Se, and Te;
R ⁷ is the same or different for each occurrence, hydrogen, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alcohol, amide sulfonate, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane Provided that at least one R ⁷ is not hydrogen,
m is 2 or 3.

In one embodiment of Formula I (a), m is 2, one R ⁷ is an alkyl group of greater than 5 carbon atoms, and all other R ⁷ are hydrogen. In one embodiment of Formula I (a), at least one R ⁷ group is fluorinated. In one embodiment, at least one R ⁷ group has at least one fluorine substituent. In one embodiment, the R ⁷ group is fully fluorinated.

In one embodiment of Formula I (a), the R ⁷ substituent on the fused alicyclic ring on the monomer improves the solubility of the monomer in water and promotes polymerization in the presence of a fluorinated acid polymer. Is done.

In one embodiment of Formula I (a), m is 2, one R ⁷ is sulfonic acid-propylene-ether-methylene, and all other R ⁷ are hydrogen. In one embodiment, m is 2, one R ⁷ is propyl-ether-ethylene, and all other R ⁷ are hydrogen. In one embodiment, m is 2, one R ⁷ is methoxy, and all other R ⁷ are hydrogen. In one embodiment, one R ⁷ is sulfonic acid difluoromethylene ester methylene (—CH ₂ —O—C (O) —CF ₂ —SO ₃ H) and all other R ⁷ are hydrogen. .

  In one embodiment, the pyrrole monomer contemplated for use to form the conductive polymer in the novel composition of the present invention is represented by the following Formula II:

In Formula II:
R ¹ is independently selected to be the same or different for each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, Amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane , Siloxane, alcohol, benzyl, carboxylate, ether, amide sulfonate, ether carboxylate, ether sulfonate, ester sulfonate And both R ¹ groups together form an alkylene chain or alkenylene chain, thereby forming a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring Formula rings can be completed, and the ring can optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms;
R ² is independently selected to be the same or different for each occurrence and is hydrogen, alkyl, alkenyl, aryl, alkanoyl, alkylthioalkyl, alkylaryl, arylalkyl, amino, epoxy, silane, siloxane, Selected from alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane.

In one embodiment, R ¹ is the same or different each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, cycloalkyl, cycloalkenyl, alcohol, benzyl, carboxylate, ether, amide sulfonate, ether carboxylate, Ether sulfonates, ester sulfonates, urethanes, epoxies, silanes, siloxanes, and one or more sulfonic acids, carboxylic acids, acrylic acids, phosphoric acids, phosphonic acids, halogens, nitro, cyano, hydroxyls, epoxies, silanes, or siloxanes Independently selected from alkyl substituted with moieties.

In one embodiment, R ² is hydrogen, alkyl, and one or more sulfonic acid, carboxylic acid, acrylic acid, phosphoric acid, phosphonic acid, halogen, cyano, hydroxyl, epoxy, silane, or siloxane moieties. Selected from substituted alkyl.

In one embodiment, the pyrrole monomer is unsubstituted and both R ¹ and R ² are hydrogen.

In one embodiment, both R ¹ together are further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Forming a 6-membered or 7-membered alicyclic ring. These groups form 6-membered or 7-membered alicyclic rings that can improve the solubility of the monomer and the resulting polymer. In one embodiment, both R ¹ together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group. In one embodiment, both R ¹ together form a 6- or 7-membered alicyclic ring, which is further substituted with an alkyl group having at least one carbon atom.

In one embodiment, both R ¹ together form —O— (CHY) _m —O—, wherein m is 2 or 3, and Y is the same or different each time it appears. Selected from hydrogen, alkyl, alcohol, benzyl, carboxylate, amidosulfonate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. In one embodiment, at least one Y group is not hydrogen. In one embodiment, at least one Y group is a substituent in which at least one hydrogen is replaced with F. In one embodiment, at least one Y group is perfluorinated.

  In one embodiment, the aniline monomer contemplated for use to form the conductive polymer in the novel composition of the present invention is represented by the following Formula III:

In the formula:
a is 0 or an integer of 1 to 4;
b is an integer from 1 to 5, provided that a + b = 5;
R ¹ is independently selected to be the same or different for each occurrence and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, Amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, cyano, hydroxyl, epoxy, silane , Siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate And both R ¹ groups together form an alkylene chain or an alkenylene chain, resulting in a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring A ring can be completed, and the ring can optionally contain one or more divalent nitrogen, sulfur, or oxygen atoms.

  Upon polymerization, the aniline monomer unit can be represented by the following formula IV (a) or formula IV (b), or a combination of both formulas:

In the formula, a, b, and R ¹ are as defined above.

  In one embodiment, the aniline monomer is unsubstituted and a = 0.

In one embodiment, a is not 0 and at least one R ¹ is fluorinated. In one embodiment, at least one R ¹ is perfluorinated.

  In one embodiment, the fused polycyclic heteroaromatic monomer contemplated for use to form the conductive polymer in the novel composition of the present invention has two or more fused aromatic rings, At least one of them is a heterocyclic aromatic. In one embodiment, the fused polycyclic heteroaromatic monomer is represented by Formula V:

In the formula:
Q is S, Se, Te, or NR ⁶ ;
R ⁶ is hydrogen or alkyl;
R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are independently selected so that each occurrence is the same or different, and hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy , Alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl, alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen , Nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, carboxylate, ether, ether carboxylate, amide sulfonate , Ether sulfonates, ester sulfonates, and urethanes;
At least one of R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , and R ¹⁰ and R ¹¹ together form an alkenylene chain to complete a 5- or 6-membered aromatic ring, Optionally, it can contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms.

  In one embodiment, the fused polycyclic heteroaromatic monomer has the formula V (a), V (b), V (c), V (d), V (e), V (f), And V (g):

In the formula:
Q is S, Se, Te, or NH;
T is the same or different at each occurrence and is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te, and PR ⁶ ;
R ⁶ is hydrogen or alkyl.
These fused polycyclic heteroaromatic monomers are further substituted with a group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. May be. In one embodiment, these substituents are fluorinated. In one embodiment, these substituents are fully fluorinated.

  In one embodiment, the fused polycyclic heteroaromatic monomer is thieno (thiophene). Such compounds are described, for example, in (Non-Patent Document 1); and (Non-Patent Document 2). In one embodiment, the thieno (thiophene) is selected from thieno (2,3-b) thiophene, thieno (3,2-b) thiophene, and thieno (3,4-b) thiophene. In one embodiment, the thieno (thiophene) monomer is further substituted with at least one group selected from alkyl, heteroalkyl, alcohol, benzyl, carboxylate, ether, ether carboxylate, ether sulfonate, ester sulfonate, and urethane. Has been. In one embodiment, these substituents are fluorinated. In one embodiment, these substituents are fully fluorinated.

  In one embodiment, the polycyclic heteroaromatic monomer contemplated for use to form the polymer in the novel composition of the present invention is represented by Formula VI:

In the formula:
Q is S, Se, Te, or NR ⁶ ;
T is selected from S, NR ⁶ , O, SiR ⁶ ₂ , Se, Te, and PR ⁶ ;
E is selected from alkenylene, arylene, and heteroarylene;
R ⁶ is hydrogen or alkyl;
R ¹² is the same or different for each occurrence, and is hydrogen, alkyl, alkenyl, alkoxy, alkanoyl, alkylthio, aryloxy, alkylthioalkyl, alkylaryl, arylalkyl, amino, alkylamino, dialkylamino, aryl Alkylsulfinyl, alkoxyalkyl, alkylsulfonyl, arylthio, arylsulfinyl, alkoxycarbonyl, arylsulfonyl, acrylic acid, phosphoric acid, phosphonic acid, halogen, nitro, nitrile, cyano, hydroxyl, epoxy, silane, siloxane, alcohol, benzyl, Carboxylate, ether, ether carboxylate, amide sulfonate, ether sulfonate, ester sulfonate, and urethane Or both R ¹² groups together form an alkylene or alkenylene chain to complete a 3, 4, 5, 6 or 7 membered aromatic or alicyclic ring And the ring can optionally contain one or more divalent nitrogen, sulfur, selenium, tellurium, or oxygen atoms.

  In one embodiment, the conductive polymer of the present invention is selected from the group consisting of thiophenes, pyrroles, thienothiophenes, and mixtures thereof.

  In one embodiment, the conductive polymer of the present invention is a copolymer of a precursor monomer and at least one second monomer. Any type of second monomer can be used provided it does not adversely affect the properties desired for the copolymer. In one embodiment, the second monomer comprises no more than 50% of the polymer based on the total number of monomer units. In one embodiment, the second monomer comprises 30% or less based on the total number of monomer units. In one embodiment, the second monomer comprises 10% or less based on the total number of monomer units.

  Representative types of the second monomer include, but are not limited to, alkenyl, alkynyl, arylene, and heteroarylene. Examples of the second monomer include, but are not limited to, fluorene, oxadiazole, thiadiazole, benzothiadiazole, phenylene vinylene, phenylene ethynylene, pyridine, diazines, and triazines, all of which are further May be substituted.

  In one embodiment, the copolymers of the present invention are prepared by first forming an intermediate precursor monomer having the structure A—B—C, where A and C may be the same or different. Represents a precursor monomer and B represents a second monomer. This ABC intermediate precursor monomer uses standard synthetic organic techniques such as Yamamoto, Stille, Grignard metathesis, Suzuki, and Negishi couplings. Can be prepared. The copolymer is then formed by oxidative polymerization of this intermediate precursor monomer alone or with one or more other precursor monomers.

  In one embodiment, the conductive polymer of the present invention is a copolymer of two or more precursor monomers. In one embodiment, these precursor monomers are selected from thiophene, selenophene, tellurophene, pyrrole, and thienothiophene.

(3. Fully fluorinated acid polymer)
The fully fluorinated acid polymer ("FFAP") of the present invention may be any polymer that is fully fluorinated and has acidic groups with acidic protons. The acidic group supplies an ionizable proton. In one embodiment, the acidic proton has a pKa of less than 3. In one embodiment, the acidic proton has a pKa of less than zero. In one embodiment, the acidic proton has a pKa of less than −5. The acidic group may be directly bonded to the polymer main chain, or may be bonded to a side chain on the polymer main chain. Examples of acidic groups include, but are not limited to, carboxylic acid groups, sulfonic acid groups, sulfonimide groups, phosphoric acid groups, phosphonic acid groups, and combinations thereof. The acidic groups can all be the same, or the polymer can have more than one type of acidic group. In one embodiment, the acidic group is selected from the group consisting of sulfonic acid groups, sulfonimide groups, and combinations thereof.

  In FFAP, the first part of the acidic group is in the form of an acidic anionic group that forms a complex with the conductive polymer. Thus, the conductive polymer is doped with FFAP. The second part of the acidic group of FFAP is in the form of a salt having a cation selected from inorganic cations, organic cations, and combinations thereof. In some cases, the third portion of the acidic group remains in the form of a protonated acid.

  In one embodiment, the FFAP of the present invention is water soluble. In one embodiment, the FFAP of the present invention is dispersible in water.

  In one embodiment, the FFAP of the present invention is wettable with organic solvents. The term “wetting with respect to an organic solvent” means a material that becomes wettable by an organic solvent when formed into a film. In one embodiment, the wettable material forms a film that is wettable by phenylhexane at a contact angle of 40 ° or less. As used herein, the term “contact angle” is intended to mean the angle Φ shown in FIG. For liquid medium droplets, the angle Φ is defined by the intersection of the surface plane and the line from the outer edge of the droplet to the surface. Furthermore, the angle Φ is measured after reaching the equilibrium position on the surface after the droplet has been applied, ie the “static contact angle”. A film of a fluorinated polymer acid that is wettable with an organic solvent is shown as the surface. In one embodiment, the contact angle is 35 ° or less. In one embodiment, the contact angle is 30 ° or less. The method for measuring the contact angle is well known.

  Examples of suitable polymer backbones include, but are not limited to, polyolefins, polyacrylates, polymethacrylates, polyimides, polyamides, polyaramids, polyacrylamides, polystyrenes, and copolymers thereof, all of which are fully fluorinated. Has been.

In one embodiment, the acidic group is a sulfonic acid group or a sulfonimide group. The sulfonimide group is represented by the following formula:
—SO ₂ —NH—SO ₂ —R
In the formula, R is an alkyl group.

  In one embodiment, the acidic group is on the fluorinated side chain. In one embodiment, the fluorinated side chain is selected from alkyl groups, alkoxy groups, amide groups, ether groups, and combinations thereof, all of which are fully fluorinated.

  In one embodiment, the FFAP of the present invention comprises a perfluorinated olefin backbone and a perfluorinated alkyl sulfonate group, a perfluorinated ether sulfonate group, a perfluorinated ester sulfonate group, or a perfluorinated ether sulfonimide group. Has a side group. In one embodiment, the polymer comprises 1,1-difluoroethylene and 2- (1,1-difluoro-2- (trifluoromethyl) aryloxy) -1,1,2,2-tetrafluoroethanesulfone. Copolymer with acid. In one embodiment, the polymer is ethylene and 2- (2- (1,2,2-trifluorovinyloxy) -1,1,2,3,3,3-hexafluoropropoxy) -1, It is a copolymer with 1,2,2-tetrafluoroethanesulfonic acid. These copolymers can be prepared as the corresponding sulfonyl fluoride polymers and can be later converted to the sulfonic acid form.

  In one embodiment, the FFAP of the present invention is a homopolymer or copolymer of fluorinated and partially sulfonated poly (arylene ether sulfone). The copolymer may be a block copolymer.

  In one embodiment, the FFAP of the present invention is a sulfonimide polymer of formula IX:

In the formula:
R _f is selected from perfluorinated alkylene, perfluorinated heteroalkylene, perfluorinated arylene, and perfluorinated heteroarylene, which may be substituted with one or more ether oxygens;
n is at least 4.

In one embodiment of Formula IX, R _f is a perfluoroalkyl group. In one embodiment, R _f is a perfluorobutyl group. In one embodiment, R _f has an ether oxygen. In one embodiment, n is greater than 10.

  In one embodiment, the FFAP of the present invention comprises a perfluorinated polymer backbone and a side chain having the formula X:

In the formula:
R ¹⁵ is a perfluorinated alkylene group or a perfluorinated heteroalkylene group;
R ¹⁶ is a perfluorinated alkyl or perfluorinated aryl group;
a is 0 or an integer of 1-4.

  In one embodiment, the FFAP of the present invention is represented by Formula XI:

In the formula:
R ¹⁶ is a perfluorinated alkyl or perfluorinated aryl group;
c is independently an integer of 0 or 1-3;
n is at least 4.

  The synthesis of FFAP is described in, for example, (Non-patent document 3); (Non-patent document 4); (Non-patent document 5); (Non-patent document 6); and Desmarteau's US Patent Publication (Patent Document 1). Are listed.

In one embodiment, the FFAP of the present invention also includes repeat units derived from at least one perfluorinated ethylenically unsaturated compound. This perfluoroolefin contains 2 to 20 carbon atoms. Typical perfluoroolefins include tetrafluoroethylene, hexafluoropropylene, perfluoro- (2,2-dimethyl-1,3-dioxole), perfluoro- (2-methylene-4-methyl-1,3- Dioxolane), CF ₂ ═CFO (CF ₂ ) _t CF═CF ₂ , where t is 1 or 2, and R _f ″ OCF═CF ₂ , where R _f ″ is 1 to 2 A saturated perfluoroalkyl group of about 10 carbon atoms), but is not limited thereto. In one embodiment, the comonomer is tetrafluoroethylene.

  In one embodiment, the FFAP of the present invention is a colloid-forming polymeric acid. As used herein, the term “colloid-forming” means a material that is insoluble in water and forms a colloid when dispersed in an aqueous medium. Colloid-forming polymeric acids typically have a molecular weight in the range of about 10,000 to about 4,000,000. In one embodiment, the polymeric acid has a molecular weight of about 100,000 to about 2,000,000. The particle size of the colloid is usually in the range of 2 nanometers (nm) to about 140 nm. In one embodiment, the colloid has a particle size of 2 nm to about 30 nm. Any fully fluorinated colloid-forming polymeric material with acidic protons can be used.

  Some of the polymers previously described herein can be formed as non-acid forms, such as salts, esters, or sulfonyl fluorides. As described below, these are converted to the acid form to prepare a conductive composition.

(4. Cation)
The cation concentration is in the range of 5 × 10 ^{−5 to} 0.2 moles of cation per gram of doped conductive polymer. In one embodiment, this concentration is 5 × 10 ^{−4 to} 0.2 moles of cation per gram of doped conductive polymer; in one embodiment, 1 × per gram of doped conductive polymer. 10 ^{−3 to} 0.2 moles of cation; in one embodiment, 1 × 10 ^{−3 to} 0.1 moles of cation per gram of doped conductive polymer.

  In one embodiment, the cation replacing the acidic proton is an organic cation. Examples of organic cations include, but are not limited to, ammonium ions substituted with one or more alkyl groups. In one embodiment, the alkyl group has 1-3 carbon atoms.

In one embodiment, the cation replacing the acidic proton is an inorganic cation. Examples of inorganic cations include, but are not limited to, ammonium and cations of groups 1 and 2 of the periodic table. In one embodiment, the inorganic cation is selected from the group consisting of NH ₄ ⁺ , Na ⁺ , K ⁺ , and combinations thereof.

(5. Preparation of doped conductive polymer composition)
In one embodiment, the doped conductive polymer composition is formed by oxidative polymerization of precursor monomers in the presence of FFAP. In one embodiment, the precursor monomer includes two or more conductive precursor monomers. In one embodiment, these monomers include intermediate precursor monomers having the structure ABC, where A and C represent conductive precursor monomers that may be the same or different. B represents a non-conductive precursor monomer. In one embodiment, the intermediate precursor monomer is polymerized with one or more conductive precursor monomers.

  In one embodiment, the oxidative polymerization is performed in a homogeneous aqueous solution. In another embodiment, the oxidative polymerization is performed in an emulsion of water and an organic solvent. In general, some water is present to obtain adequate solubility of the oxidant and / or catalyst. Oxidizing agents such as ammonium persulfate, sodium persulfate, and potassium persulfate can be used. A catalyst such as ferric chloride or ferric sulfate may also be present. The resulting polymerization product is a solution, dispersion, or emulsion of conductive polymer associated with FFAP. In one embodiment, the conducting polymer is inherently positively charged and the charge is balanced by the FFAP anion.

  In one embodiment, the process for producing an aqueous dispersion of the novel conductive polymer composition of the present invention is such that at least some FFAP is present when at least one of the precursor monomer and the oxidizing agent is added. Forming a reaction mixture by mixing water, precursor monomers, at least one FFAP, and an oxidizing agent in any order.

In one embodiment, a method for producing a doped conductive polymer composition is:
(A) providing an aqueous solution or dispersion of FFAP;
(B) adding an oxidizing agent to the solution or dispersion of step (a);
(C) adding a precursor monomer to the mixture of step (b).

  In another embodiment, the precursor monomer is added to an aqueous solution or dispersion of FFAP prior to adding the oxidizing agent. This is followed by step (b) described above in which an oxidant is added.

  In another embodiment, a mixture of water and precursor monomer is typically formed at a concentration of total precursor monomer in the range of about 0.5 wt% to about 4.0 wt%. This precursor monomer mixture is added to an aqueous solution or dispersion of FFAP, and step (b) described above in which an oxidizing agent is added is performed.

  In another embodiment, the aqueous polymerization mixture may include a polymerization catalyst such as ferric sulfate or ferric chloride. This catalyst is added before the last step. In another embodiment, the catalyst is added with an oxidant.

  In one embodiment, the polymerization is performed in the presence of a co-dispersing liquid that is miscible with water. Examples of suitable co-dispersing liquids include, but are not limited to, ethers, alcohols, alcohol ethers, cyclic ethers, ketones, nitriles, sulfoxides, amides, and combinations thereof. In one embodiment, the co-dispersing liquid is alcohol. In one embodiment, the co-dispersing liquid is an organic solvent selected from n-propanol, isopropanol, t-butanol, dimethylacetamide, dimethylformamide, N-methylpyrrolidone, and mixtures thereof. In general, the amount of co-dispersing liquid should be less than about 60% by volume. In one embodiment, the amount of co-dispersing liquid is less than about 30% by volume. In one embodiment, the amount of co-dispersing liquid is between 5-50% by volume. By using a co-dispersing liquid during the polymerization, the particle size is significantly reduced and the filterability of the dispersion is improved. Furthermore, the buffer material obtained by this method shows an increase in viscosity and the films made from these dispersions are of high quality.

  The co-dispersing liquid can be added to the reaction mixture at any point in the process of the present invention.

  In one embodiment, the polymerization is performed in the presence of a co-acid, which is a Bronsted acid. The acid may be an inorganic acid such as HCl, sulfuric acid, or an organic acid such as acetic acid or p-toluenesulfonic acid. Alternatively, the acid may be a water-soluble polymeric acid such as poly (styrene sulfonic acid), poly (2-acrylamido-2-methyl-1-propanesulfonic acid), or the second FFAP described above. A combination of these can also be used.

  The co-acid can be added to the reaction mixture at any point in the process of the present invention before any of the last added oxidant or precursor monomer is added. In one embodiment, after the co-acid is added, both the precursor monomer and FFAP are added, and finally the oxidizing agent is added. In one embodiment, after the co-acid is added, the precursor monomer is added, followed by FFAP, and finally the oxidizing agent.

  In one embodiment, the polymerization is performed in the presence of both a co-dispersing liquid and a co-acid.

  In one embodiment, first, a reaction vessel is charged with a mixture of water, an alcohol co-dispersant, and an inorganic co-acid. To this is added the precursor monomer, an aqueous solution or dispersion of FFAP, and an oxidizing agent in this order. The oxidant is dripped slowly to prevent the formation of high ionic concentration local regions that can destabilize the mixture. The mixture is stirred and then the reaction proceeds at a controlled temperature. After the polymerization is complete, the reaction mixture is treated with a strong acid cation resin, stirred and filtered; subsequently treated with a basic anion exchange resin, stirred and filtered. As noted above, another order of addition can be used.

  In the process for producing the novel conductive polymer composition of the present invention, the molar ratio of oxidizing agent to all precursor monomers is generally in the range of 0.1 to 2.0, and in one embodiment 0.4 to 1 .5. The molar ratio of FFAP to total precursor monomer is generally in the range of 0.3-10. In one embodiment, this ratio is in the range of 1-7. The total solids are generally in the range of about 0.5% to 15%, in one percent by weight, and in one embodiment in the range of about 2% to 7%. The reaction temperature is generally in the range of about 4 ° C. to 50 ° C .; in one embodiment in the range of about 20 ° C. to 35 ° C .; in one embodiment in the range of about 10 ° C. to 25 ° C. . Optionally, the molar ratio of coacid to precursor monomer used is about 0.05-4. The reaction time is generally in the range of about 1 to about 30 hours.

(6. Replacement of acidic protons with cations)
In one embodiment, the conductive polymer composition is contacted with at least one ion exchange resin under conditions suitable to replace acidic protons with cations. The composition can be processed using one or more types of ion exchange resins simultaneously or sequentially.

  Ion exchange is a reversible chemical reaction in which ions in a fluid medium (such as an aqueous dispersion) are exchanged for similar charged ions attached to fixed solid particles that are insoluble in the fluid medium. In this specification, the term “ion exchange resin” is used to mean any such substance. The resin becomes insoluble because the polymer support to which the ion exchange groups are attached has a crosslinked nature. Ion exchange resins are classified as cation exchangers or anion exchangers. Cation exchangers have positively charged mobile ions that are available for exchange and usually have metal ions such as sodium ions. Anion exchangers have negatively charged exchangeable ions, usually hydroxide ions.

  In one embodiment, the first ion exchange resin is a cationic acid exchange resin that may be in the form of metal ions, usually sodium ions. The second ion exchange resin is a basic anion exchange resin. Both acidic cation proton exchange resins and basic anion exchange resins can be used. In one embodiment, the acidic cation exchange resin is an inorganic acid cation exchange resin such as a sulfonic acid cation exchange resin. Examples of the sulfonic acid cation exchange resin considered for use in the practice of the present invention include sulfonated styrene-divinylbenzene copolymer, sulfonated crosslinked styrene polymer, phenol-formaldehyde-sulfonic acid resin, and benzene-formaldehyde-sulfonic acid resin. , And mixtures thereof. In another embodiment, the acidic cation exchange resin is an organic acid cation exchange resin, such as a carboxylic acid, acrylic acid, or phosphorous acid cation exchange resin. In addition, a mixture of different cation exchange resins can be used.

  In another embodiment, the basic anion exchange resin is a tertiary amine anion exchange resin. Examples of the tertiary amine anion exchange resin to be used in the practice of the present invention include tertiary aminated styrene-divinylbenzene copolymer, tertiary aminated crosslinked styrene polymer, tertiary aminated phenol- These include formaldehyde resins, tertiary aminated benzene-formaldehyde resins, and mixtures thereof. In yet another embodiment, the basic anion exchange resin is a quaternary amine anion exchange resin, or a mixture of these and other exchange resins.

  In one embodiment, both types of resins are added simultaneously to a liquid composition comprising a conductive polymer and FFAP and contacted with the liquid composition for at least about 1 hour, such as from about 2 hours to about 20 hours. To maintain. Next, the ion exchange resin can be removed from the dispersion by filtration. The size of the filter is selected such that relatively large ion exchange resin particles are removed and smaller dispersed particles pass through. Generally, about 1 to 5 grams of ion exchange resin is used per gram of new conductive polymer composition.

  In some embodiments, acidic protons are replaced by adding a basic aqueous solution. Basic compounds include hydroxides, carbonates, and bicarbonates. Examples of the solution include, but are not limited to, sodium hydroxide, ammonium hydroxide, tetramethylammonium hydroxide and the like.

  In one embodiment, more than 50% of the acidic protons are replaced with cations. In one embodiment, more than 60% substitutions; in one embodiment, more than 75% substitutions; in one embodiment, more than 90% substitutions.

(7. Electronic devices)
In another embodiment of the invention, an electronic device is provided that includes at least one layer made of the conductive polymer composition described herein. The term “electronic device” is intended to mean a device comprising one or more organic semiconductor layers or organic semiconductor materials. Electronic devices include: (1) devices that convert electrical energy into radiation (eg, light emitting diodes, light emitting diode displays, diode lasers, or lighting panels), (2) devices that detect signals via electronic processes (eg, (3) devices that convert radiation into electrical energy (eg, photovoltaics), photo detectors, photoconductive cells, photo resistors, photo switches, phototransistors, phototubes, infrared (“IR”) detectors, or biosensors) Electrical devices or solar cells), (4) devices comprising one or more electronic components comprising one or more organic semiconductor layers (e.g. transistors or diodes), or in items (1) to (4) Any combination of devices, but not limited to No.

  In one embodiment, the electronic device of the present invention includes at least one electroactive layer disposed between two electrical contact layers, the device further including a bilayer. The term “electroactive” when referring to a layer or material is intended to mean a layer or material that exhibits electronic or electro-radiative properties. The electroactive layer material may emit radiation or may exhibit a change in the concentration of electron-hole pairs when receiving radiation.

  As shown in FIG. 2, the exemplary device 100 has an anode layer 110, a buffer layer 120, an optional electroactive layer 130, an electroactive layer 140, an optional electron injection / transport layer 140, and a cathode layer 160. .

  The device can include a support or substrate (not shown) that can be adjacent to the anode layer 110 or the cathode layer 160. In most cases, the support is adjacent to the anode layer 110. The support may be flexible or rigid, and may be organic or inorganic. Examples of support materials include, but are not limited to glass, ceramic, metal, and plastic films.

  The anode layer 110 is an electrode that is more efficient in injecting holes than the cathode layer 160. The anode can include materials containing metals, mixed metals, alloys, metal oxides, or mixed oxides. Suitable materials include Group 2 elements (ie, Be, Mg, Ca, Sr, Ba, Ra), Group 11 elements, Group 4, Group 5, and Group 6 elements, and Examples include mixed oxides of Group 10 transition elements. In order to make the anode layer 110 light transmissive, a mixed oxide of elements of Group 12, 13, and 14, such as indium tin oxide, can be used. As used herein, the phrase “mixed oxide” has a Group 2 element or two or more different cations selected from Group 12, Group 13, or Group 14 elements. Means oxide. Some non-limiting examples of materials for the anode layer 110 include indium tin oxide (“ITO”), indium zinc oxide, aluminum tin oxide, gold, silver, copper, and nickel. Although it is mentioned, it is not limited to these. The anode can also include organic materials, particularly conductive polymers such as polyaniline, for example, the representative materials described in (Non-Patent Document 7). At least one of the anode and cathode should be at least partially transparent so that the generated light can be observed.

  The anode layer 110 can be formed by chemical vapor deposition, physical vapor deposition, or spin coating. Chemical vapor deposition can be performed as plasma enhanced chemical vapor deposition (“PECVD”) or metal organic chemical vapor deposition (“MOCVD”). Physical vapor deposition can include all forms of sputtering, such as ion beam sputtering, as well as e-beam evaporation and resistance evaporation. Specific forms of physical vapor deposition include radio frequency magnetron sputtering and inductively coupled plasma physical vapor deposition (“IMP-PVD”). These deposition techniques are well known in the semiconductor manufacturing field.

  In one embodiment, the anode layer 110 is patterned during a lithographic operation. This pattern can be changed as needed. These layers can be patterned, such as by placing a patterned mask or resist on the first flexible composite barrier structure before applying the first electrical contact layer material. . Alternatively, these layers can be applied as an entire layer (also called blanket deposition), followed by patterning using, for example, a patterned resist layer and wet chemical or dry etching techniques can do. Other patterning methods well known in the art can also be used.

  The conductive polymer composition described herein is suitable as the buffer layer 120. The term “buffer layer” or “buffer material” is intended to mean a conductive or semiconducting material, which includes, but is not limited to, planarization of the underlying layer, charge transport and / or One or more functions can be included in the organic electronic device, such as charge injection properties, trapping of impurities such as oxygen or metal ions, and other features that facilitate or improve the performance of the organic electronic device. The buffer layer is deposited on the substrate using a wide variety of techniques well known to those skilled in the art. Typical deposition techniques include vapor deposition, liquid deposition (continuous and discontinuous techniques), and thermal transfer. Continuous deposition techniques include, but are not limited to, spin coating, gravure coating, curtain coating, dip coating, slot die coating, spray coating, and continuous nozzle coating. Discontinuous deposition techniques include, but are not limited to, ink jet printing, gravure printing, and screen printing.

  An optional layer 130 can be present between the buffer layer 120 and the electroactive layer 140. This layer can include a hole transport material. Examples of hole transport materials are summarized in (Non-patent Document 8), for example. Both hole transport molecules and hole transport polymers can be used. Commonly used hole transport molecules include: 4,4 ′, 4 ″ -tris (N, N-diphenyl-amino) -triphenylamine (TDATA); 4,4 ′, 4 ″ -tris (N -3-methylphenyl-N-phenyl-amino) -triphenylamine (MTDATA); N, N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4 , 4′-diamine (TPD); 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (TAPC); N, N′-bis (4-methylphenyl) -N, N′-bis (4 -Ethylphenyl)-[1,1 ′-(3,3′-dimethyl) biphenyl] -4,4′-diamine (ETPD); tetrakis- (3-methylphenyl) -N, N, N ′, N ′ -2,5-phenylenediamine (PDA); α-phenyl-4-N, N-diphenylaminostyrene (TPS); p- (diethylamino) benzaldehyde diphenylhydrazone (DEH); triphenylamine (TPA); bis [4- (N, N-diethylamino) ) -2-methylphenyl] (4-methylphenyl) methane (MPMP); 1-phenyl-3- [p- (diethylamino) styryl] -5- [p- (diethylamino) phenyl] pyrazoline (PPR or DEASP); 1,2-trans-bis (9H-carbazol-9-yl) cyclobutane (DCZB); N, N, N ′, N′-tetrakis (4-methylphenyl)-(1,1′-biphenyl) -4, 4′-diamine (TTB); N, N′-bis (naphthalen-1-yl) -N, N′-bis- (phenyl) base And porphyrin compounds such as copper phthalocyanine, but are not limited thereto. Commonly used hole transport polymers include, but are not limited to, polyvinylcarbazole, (phenylmethyl) polysilane, poly (dioxythiophene), polyaniline, and polypyrrole. Hole transport polymers can also be obtained by doping hole transport molecules such as those described above into polymers such as polystyrene and polycarbonate.

  In some embodiments, the hole transport layer comprises a hole transport polymer. In some embodiments, the hole transport polymer is a distyrylaryl compound. In some embodiments, the aryl group has two or more fused aromatic rings. In certain embodiments, the aryl group is acene. As used herein, the term “acene” refers to a hydrocarbon parent component having two or more ortho-fused benzene rings in a linear array.

  In some embodiments, the hole transport polymer is an arylamine polymer. In some embodiments, this is a copolymer of fluorene monomer and arylamine monomer.

  In some embodiments, the polymer has crosslinkable groups. In some embodiments, it can be crosslinked by heat treatment and / or exposure to UV or visible light. Examples of crosslinkable groups include, but are not limited to, vinyl, acrylate, perfluorovinyl ether, 1-benzo-3,4-cyclobutane, siloxane, and methyl ester. Crosslinkable polymers can have advantages in the production of solution process OLEDs. The use of a soluble polymer material to form a layer that can be converted to an insoluble film after deposition allows the production of multilayer solution processed OLED devices that do not suffer from layer dissolution problems.

  Examples of crosslinkable polymers can be found in, for example, US Patent Publications (Patent Document 2) and (Patent Document 3).

  In some embodiments, the hole transport layer comprises a polymer that is a copolymer of 9,9-dialkylfluorene and triphenylamine. In some embodiments, the polymer is a copolymer of 9,9-dialkylfluorene and 4,4'-bis (diphenylamino) biphenyl. In some embodiments, the polymer is a copolymer of 9,9-dialkylfluorene and TPB. In some embodiments, the polymer is a copolymer of 9,9-dialkylfluorene and NPB. In some embodiments, the copolymer is made from a third copolymer selected from (vinylphenyl) diphenylamine and 9,9-distyrylfluorene or 9,9-di (vinylbenzyl) fluorene.

  Depending on the device application, the electroactive layer 140 is a light emitting layer (such as in a light emitting diode or light emitting electrochemical cell) that is activated by an applied voltage, responsive to radiant energy, with or with the application of a bias voltage. Rather, it may be a layer of material that generates a signal (such as in a photodetector). In one embodiment, the electroactive material is an organic electroluminescent (“EL”) material. Any EL material such as, but not limited to, small molecule organic fluorescent compounds, fluorescent and phosphorescent metal complexes, conjugated polymers, and mixtures thereof can be used in the device. Examples of fluorescent compounds include, but are not limited to, pyrene, perylene, rubrene, coumarin, derivatives thereof, and mixtures thereof. Examples of metal complexes include metal chelated oxinoid compounds such as tris (8-hydroxyquinolato) aluminum (Alq3); Petrov et al., US Patent Publication (Patent Literature 4), and Patent Literature 5 and Patent Literature. And iridium and platinum electroluminescent compounds such as iridium complexes having a phenylpyridine ligand, a phenylquinoline ligand, or a phenylpyrimidine ligand, as disclosed in US Pat. 7, organometallic complexes as described in Patent Document 8 and Patent Document 9, and mixtures thereof, but are not limited thereto. An electroluminescent light-emitting layer comprising a charge transport host material and a metal complex has been described in US Pat. No. 5,956,086 by Thompson et al., And US Pat. Are listed. Examples of conjugated polymers include, but are not limited to, poly (phenylene vinylene), polyfluorene, poly (spirobifluorene), polythiophene, poly (p-phenylene), copolymers thereof, and mixtures thereof. It is not a thing.

The optionally used layer 150 may serve to facilitate both electron injection / transport and may function as a confinement layer to prevent quenching reactions at the layer interface. More specifically, layer 140 can facilitate electron transfer and reduce the likelihood of quenching reactions when layers 140 and 160 are in direct contact without this layer. Examples of optional layer 150 materials include bis (2-methyl-8-quinolinolato) (p-phenyl-phenolato) aluminum (III) (BAlQ) and tris (8-hydroxyquinolato) aluminum (Alq). ₃ ) metal chelated oxinoid compounds; tetrakis (8-hydroxyquinolinato) zirconium; 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD) ), 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole (TAZ) and 1,3,5-tri (phenyl-2-benzimidazole) ) Azole compounds such as benzene (TPBI); Kinoki such as 2,3-bis (4-fluorophenyl) quinoxaline Phosphorus derivatives; phenanthroline derivatives such as 9,10-diphenylphenanthroline (DPA) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (DDPA); and any combination of one or more thereof However, it is not limited to these. Alternatively, the optional layer 150 may be inorganic and can include BaO, LiF, Li ₂ O, and the like.

  The cathode layer 160 is an electrode that is particularly effective for injecting electrons or negative charge carriers. Cathode layer 160 may be any metal or non-metal having a lower work function than the first electrical contact layer (in this case, anode layer 110). As used herein, the term “low work function” is intended to mean a material having a work function of about 4.4 eV or less. As used herein, “high work function” is intended to mean a material having a work function of at least about 4.4 eV.

  Cathode layer materials include Group 1 alkali metals (eg, Li, Na, K, Rb, Cs), Group 2 metals (eg, Mg, Ca, Ba, etc.), Group 12 metals, lanthanides (eg, Ce, Sm, Eu, etc.), and actinides (eg, Th, U, etc.). Materials such as aluminum, indium, yttrium, and combinations thereof can also be used. Non-limiting specific examples of cathode layer 160 materials include, but are not limited to, barium, lithium, cerium, cesium, europium, rubidium, yttrium, magnesium, samarium, and alloys and combinations thereof. is not.

  In general, the cathode layer 160 is formed by chemical vapor deposition or physical vapor deposition. In some embodiments, a pattern is formed in the cathode layer as described above for the anode layer 110.

  The other layers in the device may be made of any material known to be useful for such layers by considering the function that such layers are to perform.

  In certain embodiments, an encapsulation layer (not shown) is deposited over the contact layer 160 to prevent unwanted components such as water and oxygen from entering the device 100. Such components may adversely affect the organic layer 140. In one embodiment, the encapsulation layer is a barrier layer or membrane. In one embodiment, the encapsulating layer is a glass lid.

  Although not shown, it should be understood that the device 100 can include additional layers. Other layers known in the art or other fields can be used. Further, any of the above layers can include two or more sublayers, and can also form a layered structure. Alternatively, some or all of the layers can be treated to improve charge carrier transport efficiency or other physical properties of the device, particularly surface treatments. The choice of material for each component layer preferably provides a device with high device efficiency, manufacturing time, and complex factors that take into account the device's operational life, as well as other important issues recognized by those skilled in the art To be determined to balance multiple goals. It should be understood that the determination of optimal components, component configurations, and compositions is a routine task of those skilled in the art.

  In one embodiment, the various layers of the present invention have a thickness in the following range: anode 110 is 500-5000 mm, in one embodiment 1000-2000 mm; buffer layer 120 is 50-2000 mm, one In embodiments, 200-1000 Å; optional hole transport layer 130 is 50-2000 Å, in one embodiment 200-1000 Å; photoactive layer 140 is 10-2000 Å, in one embodiment 100-1000 Å; The electron transport layer 150 is 50 to 2000 mm, in one embodiment 100 to 1000 mm; the cathode 160 is 200 to 10,000 mm, and in one embodiment 300 to 5000 mm. The location of the electron-hole recombination region in the device, and thus the emission spectrum of the device, can be affected by the relative thickness of each layer. For example, the thickness of the electron transport layer should be selected such that an electron-hole recombination zone is present in the light emitting layer. The desired ratio of layer thickness depends on the exact nature of the material used.

  In operation, a voltage from an appropriate power source (not shown) is applied to device 100. Thereby, current flows through the layers of the device 100. As a result, current flows through the entire layer of device 100. Electrons enter the organic polymer layer and emit photons. In some OLEDs, called active matrix OLED displays, individual deposits of photoactive organic film can be independently excited by the flow of current, thereby allowing individual pixels to emit light. In some OLEDs, referred to as passive matrix OLED displays, photoactive organic film deposits can be excited by rows and columns of electrical contact layers.

  The concepts described herein are illustrated in more detail in the following examples, which do not limit the scope of the invention described in the claims.

(Comparative Example A)
This comparative example shows the effect of pH on device performance when using Baytron-P (registered trademark) AI4083 as a buffer layer.

Baytron-P AI4083 (HC Starck, GmbH, Leverkuson, Germany) is a poly (3,4-dioxy-ethylenethiophene) / poly ( Styrene sulfonic acid), ie PEDOT / PSSA. The sample in the obtained state of Baytron-P AI4083 was measured and had a PEDOT / PSSA of 1.5% (w / w) solids and a pH of 1.7 (Comparative Example A-1). Until about pH 2.6, about 1.0 M NH ₄ OH aqueous solution was added to about 100 g of Bytron-P (Comparative Example A-2). The pH of another 100 g of Baytron-P was adjusted to 3.9 (Comparative Example A-3).

Comparative Examples A-1, A-2, and A-3 were spin coated on a glass / ITO backlight substrate (30 mm × 30 mm). Each ITO substrate having an ITO thickness of 100 to 150 nm is composed of three 5 mm × 5 mm pixels and one 2 mm × 2 mm pixel for light emission. After spin coating on the ITO substrate, the resulting film was first baked in air at 130 ° C. for 10 minutes and then at 200 ° C. for 10 minutes. The thickness of the Baytron-P (Baytron-P) layer after baking was 40 nm. The Baytron-P layer has a thickness of about 60 nm of Dow Chemicals Lumination Green 1303 electroluminescent polymer (from a 1% w / v solution in p-xylene). The film was spin coated in air. After this electroluminescent film was baked in a dry box at 130 ° C. for 30 minutes, a cathode composed of 3 nm of Ba and 260 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ⁻⁶ Torr. The device was encapsulated by bonding a glass slide on the back of the device using a UV curable epoxy resin.

Table 1 shows 200, 500, 1,000, and 2,000 nits (Cd / m) of devices made using Baytron-P® AI4083 buffer layers at three different pHs. The light emitting device efficiency in ² ) is shown. This data shows that with all three pH Baytron-P, increasing the brightness from 200 nits to 2,000 nits, the efficiency increases slowly. As the pH increases, the efficiency decreases, indicating an adverse effect of pH on device performance.

Example 1
This example illustrates the cationic composition of low pH poly (3,4-dioxyethylenethiophene) (PEDOT) / Nafion® (poly (tetrafluoroethylene) / perfluoroether sulfonic acid)) The comparison between the product and device performance and Vitron-P of Comparative Example A is shown.

  A dispersion of polydioxythiophene and colloid-forming polymer acid made using PEDOT and the commercial product Nafion® available from the present applicant has an EW (acid equivalent). An aqueous Nafion® colloidal dispersion that was 1000 was used. 25% (w / w) Nafion (R) dispersion in a procedure similar to that of Example 1 Part 2 of US Patent Publication (Patent Document 13) except that the temperature was about 270 <0> C. The body was made and then diluted with water to obtain a 12.0% (w / w) dispersion for polymerization.

  1,2-ethylenedioxythiophene (“EDOT”) monomer was reacted with the Nafion® dispersion as described in US Pat.

After completion of the reaction for about 18.5 hours, each 200 g of Dowex M31, and Dowex M43 ion exchange resin, and 225 g of deionized water were added to the reaction mixture and stirred at 120 RPM for 4 hours. Finally, the ion exchange resin was filtered from the suspension using VWR 417 filter paper. The entire filtered dispersion was pumped through the orifice at once at 5.000 psi. The pH of this dispersion was 1.9, and the conductivity of the film spin-coated from the dispersion and baked at 130 ° C. was 9.4 × 10 ⁻³ S / cm at room temperature.

The dispersion was found to contain 5.34% total solids consisting essentially of PEDOT and Nafion®. Ion chromatographic analysis shows that this dispersion contains only 62.7 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to about 3.5 × 10 ⁻⁶ moles of NH ₄ ⁺ per gram of dispersion. Therefore, the cation concentration was 0.7 × 10 ⁻⁴ mol NH ₄ ⁺ per gram of solids (total of PEDOT and Nafion®). The ammonium cation is the residual amount from the ammonium persulfate oxidant. Based on% solids and the amount of Nafion® used during polymerization, the dispersion contains about 51 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. This shows that about 15% of the sulfonic acid groups form an ammonium salt in the solid content. Some of the remaining sulfonate anion forms a complex with partially oxidized poly (3,4-ethylenedioxythiophene) (PEDOT) to balance the positive charge on the PEDOT backbone. It is reasonable to assume that about 3.5 EDOT units are one electron deficient. The total number of EDOT used during the polymerization is 14.6 × 10 ⁻⁶ per gram of dispersion. Therefore, it is estimated that 4.2 × 10 ⁻⁶ moles of sulfonic acid groups are used as anions to balance the partially oxidized PEDOT. This still leaves about 80% of the sulfonic acid as an acid in the solids. It should be understood that the ammonium cation can be completely removed by further processing using a proton exchange resin.

According to the procedure shown in Comparative Example A, the above PEDOT / Nafion® at pH 1.9 was incorporated into a light emitting device. The thickness of the PEDOT / Nafion® film initially baked at 130 ° C. for 10 minutes in air and then baked at 200 ° C. for 10 minutes was 70 nm. The thickness of Lumination Green 1303 baked at 130 ° C. for 30 minutes in a dry box was 60 nm. A cathode composed of 3 nm of Ba and 260 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ⁻⁶ Torr. The device was encapsulated by bonding a glass slide on the back of the device using a UV curable epoxy resin.

  The device data for this example summarized in Table 1 shows that PEDOT / Nafion® at pH 1.9 increases immediately to high efficiency at low brightness. Also, using Luminance Green 1303 provides much higher efficiencies than Baytron-P at all pH values. Table 1 shows the lifetime of T-50 (the luminance drops to half of 5,050 nits of the original luminance). Table 1 also shows that PEDOT / Nafion® maintains high efficiency regardless of pH and cation concentration.

(Example 2)
This example demonstrates the cationic composition and device performance of poly (3,4-dioxy-ethylenethiophene) / Nafion® prepared in Example 1 and adjusted to pH 6.4 with aqueous NaOH. .

The PEDOT / Nafion® dispersion produced in Example 1 contains 5.34% solids and has a pH of 1.9. To about 200 ml of this dispersion was added 1N aqueous sodium hydroxide solution until the pH reached 6.4. This dispersion was found to contain 5.33% solids by measurement. The conductivity of the film spin-coated from this pH 6.4 dispersion and baked at 130 ° C. is 2.9 × 10 ⁻⁴ S / cm at room temperature. Ion chromatography analysis shows that this dispersion contains 963 × 10 ⁻⁶ g Na ⁺ and 70.6 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to approximately 42 × 10 ⁻⁶ moles of Na ⁺ and 3.9 × 10 ⁻⁶ moles of NH ₄ ⁺ per gram of dispersion, so the total cation concentration is equivalent to 1 gram of dispersion. It was 46 × 10 ⁻⁶ mol (NH ₄ ⁺ and Na ⁺ ) per unit. Therefore, the total cation concentration was 8.6 × 10 ⁻⁴ moles of cation (mainly Na ⁺ ) per gram of solids (total of PEDOT and Nafion®). Based on% solids and the amount of Nafion® used during polymerization, the dispersion contains about 51 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. This shows that about 90% of the sulfonic acid groups form sodium and ammonium salts in the solids. Some of the remaining sulfonate anion forms a complex with partially oxidized 3,4-ethylenedioxythiophene (EDOT) to balance the positive charge. It is reasonable to assume that about 3.5 EDOT units are one electron deficient. The total number of EDOT used during the polymerization is 14.6 × 0 ⁻⁶ moles per gram of dispersion. Therefore, it is estimated that 4.2 × 10 ⁻⁶ moles of sulfonic acid is used as an anion to balance the partially oxidized poly (EDOT). This leaves only 2% of the sulfonic acid as an acid in the solids.

  According to the procedure shown in Comparative Example A and Example 1, Lumination Green 1303 was used to obtain the above PEDOT / Nafion® at pH 6.4 containing mainly sodium cations. Built into the light emitting device. The device data for this example summarized in Table 1 shows that PEDOT / Nafion (R), adjusted from low pH to pH 6.4 using sodium cation, also increases immediately to high efficiency at low brightness. It shows that Also, using Luminance Green 1303 provides much higher efficiencies than Baytron-P at all pH values. Table 1 shows the lifetime of T-50 (the brightness drops to half of the original brightness of 4,420 nits). Table 1 also shows that PEDOT / Nafion® maintains high efficiency regardless of pH and cation concentration.

(Example 3)
This example is a poly (3,4-dioxy-ethylenethiophene) / Nafion® cation composition prepared in Example 1 and adjusted to pH 6.4 with aqueous NH ₄ OH and device performance. Indicates.

The PEDOT / Nafion® dispersion produced in Example 1 contains 5.34% solids and has a pH of 1.9. To about 200 ml of this dispersion was added 1N aqueous ammonium hydroxide solution until the pH reached 6.4. The dispersion was found to contain 5.49% solids by measurement. The conductivity of the membrane derived from this pH 6.4 dispersion and baked at 130 ° C. is 6.8 × 10 ⁻⁴ S / cm at room temperature. Ion chromatographic analysis shows that this dispersion contains 745 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to about 41 × 10 ⁻⁶ moles of NH ₄ ⁺ per gram of dispersion. Thus, the cation concentration was 7.7 × 10 ⁻⁴ moles NH ₄ ⁺ per gram of solids (total of PEDOT and Nafion®). Based on% solids and the amount of Nafion® used during polymerization, the dispersion contains about 53 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. This shows that about 77% of the sulfonic acid groups form an ammonium salt in the solid content. Some of the remaining sulfonate anion forms a complex with partially oxidized 3,4-ethylenedioxythiophene (EDOT) to balance the positive charge. It is reasonable to assume that about 3.5 EDOT units are one electron deficient. The total number of EDOT used during the polymerization is 15.1 × 10 ⁻⁶ moles per gram of dispersion. Therefore, it is estimated that 4.3 × 10 ⁻⁶ moles of sulfonic acid is used as an anion to balance the partially oxidized poly (EDOT). This leaves about 15% of the sulfonic acid as an acid in the solids.

  Luminescence Green 1303 is used to emit PEDOT / Nafion (registered trademark) at pH 6.4 containing the above ammonium cation using the procedure shown in Comparative Example 1 and Example 1. Built into the device. The device data for this example summarized in Table 1 shows that PEDOT / Nafion®, adjusted from low to high pH using ammonium cations, immediately increases to high efficiency at low brightness. It is shown that. Also, using Luminance Green 1303 provides much higher efficiencies than Baytron-P at all pH values. Table 1 shows the lifetime of T-50 (the luminance decreases to half of the original luminance of 4,630 nits). Table 1 also shows that PEDOT / Nafion® maintains high efficiency regardless of pH and cation concentration.

(Example 4)
This example demonstrates the cationic composition and device performance of low pH polypyrrole / poly (tetrafluoroethylene / perfluoroether sulfonic acid) (“PPy / Nafion®”).

  The PPy / Nafion® dispersion used in this example was prepared using an aqueous Nafion® colloidal dispersion with an EW (acid equivalent) of 1000. 25% (w / w) Nafion (R) dispersion in a procedure similar to that of Example 1 Part 2 of US Patent Publication (Patent Document 13) except that the temperature was about 270 <0> C. The body was made and then diluted with water to obtain a 12.0% (w / w) dispersion for polymerization.

  A pyrrole (“Py”) monomer was reacted with a Nafion® dispersion as described in US Pat.

After completion of the reaction for about 29 hours, each 100 g of Dowex M31 and Dowex M43 ion exchange resin and 100 g of deionized water were added to the reaction mixture, which was stirred at 120 RPM for 2 hours. Finally, the ion exchange resin was filtered from the suspension using VWR 417 filter paper. The pH of this dispersion was 2.35, and the conductivity of the film spin-coated from the dispersion and baked at 130 ° C./10 minutes was 5.4 × 10 ⁻² S / cm at room temperature.

This dispersion was found to contain 3.88% PPy / Nafion® solids by measurement. Ion chromatographic analysis shows that this dispersion contains only 93.4 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to about 5.2 × 10 ⁻⁶ moles of NH ₄ ⁺ per gram of dispersion. Thus, the cation concentration was 1.3 × 10 ⁻⁴ mol NH ₄ ⁺ per gram of solids (PPy + Nafion® total). The ammonium cation is the residual amount from the ammonium persulfate oxidant. Based on% solids and the amount of Nafion® used during polymerization, the dispersion contains about 36.4 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. . This shows that about 14% of the sulfonic acid groups form ammonium salts in the solid content. A portion of the remaining sulfonate anion forms a complex with the partially oxidized polypyrrole to balance the positive charge. It is estimated that about 3.5 pyrrole units are one electron deficient. The total number of pyrroles used during the polymerization is 36.4 × 10 ⁻⁶ moles per gram of dispersion. Therefore, it is estimated that 10 × 10 ⁻⁶ moles of sulfonic acid groups are used as anions to balance the partially oxidized polypyrrole. This still leaves 42% of the sulfonic acid as an acid in the solids. It should be understood that the ammonium cation can be completely removed by further processing using a proton exchange resin.

In accordance with the procedure shown in Comparative Example 1 and Example 1, Luminescence Green 1303 was used to incorporate pH 2.3 PPy / Nafion® into the light emitting device. The thickness of the PPy / Nafion® film initially baked at 130 ° C. for 10 minutes in air and then baked at 200′C for 10 minutes in nitrogen was 47 nm. The thickness of Lumination Green 1303 baked at 130 ° C. for 30 minutes in a dry box was 60 nm. A cathode composed of 3 nm of Ba and 240 nm of Al was thermally evaporated at a pressure of less than 4 × 10 ⁻⁶ Torr. The device was encapsulated by bonding a glass slide on the back of the device using a UV curable epoxy resin. The device data for this example summarized in Table 1 shows that the pH 2.3 PPy / Nafion® is much more efficient than Baytron-P at all pH values. It shows that a Luminance Green 1303 device is obtained. Table 1 shows the lifetime of T-50 (the brightness drops to half of 2,600 nits of the original brightness). Table 1 also shows that, unlike Baytron-P, PPy / Nafion® containing sodium or ammonium cations at higher pH has higher device efficiency. ing.

(Example 5)
This example shows the cation composition and device performance of PPy / Nafion® made in Example 4 and adjusted to pH 6.4 with aqueous NaOH.

The PPy / Nafion® dispersion made in Example 4 contains 3.88% solids and has a pH of 2.3. To the approximately 200 ml of this dispersion was added 1N aqueous sodium hydroxide solution until the pH reached 6.4. The dispersion was found to contain 3.86% solids by measurement. The conductivity of the film spin-coated from this pH 6.4 dispersion and baked at 130 ° C. is 1.7 × 10 ⁻³ S / cm at room temperature. Ion chromatographic analysis shows that this dispersion contains 511.8 × 10 ⁻⁶ g Na ⁺ and 76.6 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to approximately 22.3 × 10 ⁻⁶ moles Na ⁺ and 4.2 × 10 ⁻⁶ moles NH ₄ ⁺ per gram of dispersion at pH 6.4, or a total of 27 × 10 Corresponds to ^-6 mol total cations (Na ⁺ and NH ₄ ⁺ ). Thus, the cation concentration was 7 × 10 ⁻⁴ moles of total cation (primarily Na ⁺ ) per gram of solids (PPy + Nafion® total). Based on percent solids and the amount of Nafion® used during polymerization, the dispersion contains about 36.2 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. . This shows that about 73% of the sulfonic acid groups form sodium and ammonium salts in the solids. A portion of the remaining sulfonate anion forms a complex with the partially oxidized polypyrrole to balance the positive charge. It is reasonable to assume that approximately 3.5 PPy units are one electron deficient. The total amount of PPy used during the polymerization is 36.2 × 10 ⁻⁶ moles per gram of dispersion. Therefore, it is estimated that 10.3 × 10 ⁻⁶ moles of sulfonic acid is used as an anion to balance the partially oxidized polypyrrole. For this reason, about 0% of the sulfonic acid remains as an acid in the solid content.

  According to the procedure shown in Comparative Example 1 and Example 1, using Lumination Green 1303, PPy / Nafion (registered trademark) having pH 6.4 containing mainly sodium cation as described above was used. Built into the light emitting device. The device data summarized in Table 1 shows that PPy / Nafion (R) adjusted from low to high pH using sodium cations also increases to high efficiency at low brightness. . Also, a Luminance Green 1303 device is obtained that is much more efficient than Baytron-P at all pH values. Table 1 shows the lifetime of T-50 (the brightness drops to half of 2,900 nits of the original brightness). Table 1 also shows that, unlike Baytron-P, PPy / Nafion® containing sodium or ammonium cations at high pH has higher device efficiency. ing.

(Example 6)
This example shows the cationic composition and device performance of polypyrrole / Nafion® prepared in Example 1 and adjusted to pH 6.4 with aqueous NH ₄ OH.

The PPy / Nafion® dispersion made in Example 3 contains 3.88% solids and has a pH of 2.3. About 200 ml of this dispersion was added 1N aqueous ammonium hydroxide solution until the pH reached 6.4. The dispersion was found to contain 3.81% solids by measurement. The conductivity of the film obtained from this pH 6.4 dispersion and baked at 130 ° C. is 1.6 × 10 ⁻³ S / cm at room temperature. Ion chromatographic analysis shows that this dispersion contains 447.8 × 10 ⁻⁶ g NH ₄ ⁺ per mL of dispersion. The ion concentration corresponds to about 24.8 × 10 ⁻⁶ moles of NH ₄ ⁺ per gram of dispersion at pH = 6.4. Therefore, the cation concentration was 6.4 × 10 ⁻⁴ moles NH ₄ ⁺ per gram of solids (PPy + Nafion® total). Based on% solids and the amount of Nafion® used during polymerization, this dispersion contains about 35.7 × 10 ⁻⁶ moles of sulfonic acid groups per gram of dispersion. . This shows that about 69.5% of the sulfonic acid groups form an ammonium salt in the solid content. A portion of the remaining sulfonate anion forms a complex with the partially oxidized polypyrrole to balance the positive charge. It is reasonable to assume that about 3.5 pyrrole units are one electron deficient. The total number of pyrroles used during the polymerization is 35.7 × 10 ⁻⁶ moles per gram of dispersion. Therefore, it is estimated that 10.2 × 10 ⁻⁶ moles of sulfonic acid groups are used as anions to balance the partially oxidized polypyrrole. For this reason, about 0% of the sulfonic acid remains as an acid in the solid content.

  Luminescence Green 1303 is used to emit PPy / Nafion® at pH 6.4 containing the above ammonium cation using the procedure shown in Comparative Example 1 and Example 1. Built into the device. The device data summarized in Table 1 shows that PPy / Nafion (R) adjusted from low to high pH using ammonium cations also increases to high efficiency at low brightness. . Also, a Luminance Green 1303 device is obtained that is much more efficient than Baytron-P at all pH values. Table 1 shows the lifetime of T-50 (the brightness drops to half of 3,350 nits of the original brightness). Table 1 also shows that, unlike Baytron-P, PPy / Nafion® containing sodium or ammonium cations at high pH has higher device efficiency. ing.

  Not all acts described above in the summary or example are required and some of the specific acts may not be necessary, and one or more additional actions may be performed in addition to the actions described above. Please note that there may be cases. Further, the order in which actions are listed are not necessarily the order in which they are performed.

  In the foregoing specification, the concepts of the invention have been described with reference to specific embodiments. However, one of ordinary skill in the art appreciates that various modifications and changes can be made without departing from the scope of the present invention as set forth in the claims below. The specification and drawings are, accordingly, to be regarded in an illustrative rather than a restrictive sense, and all such modifications are intended to be included within the scope of the present invention.

  Benefits, other advantages, and solutions to problems have been described above with regard to specific embodiments. However, these benefits, benefits, solutions to problems, and any features that may cause or make any benefit, advantage, or solution any of the claims or It is not intended to be interpreted as all important, necessary, or essential features.

  It should be understood that in the context of separate embodiments, the specific features described herein for clarity may be provided in combination in one embodiment. Conversely, the various features described in the context of one embodiment for the sake of brevity can also be provided separately or in any sub-combination. Further, reference to values stated in a range include all values within that range.

It is a figure which shows a contact angle. It is the schematic of an organic electronic device.

Claims (7)

A conductive polymer composition comprising a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups, wherein the first portion of the acidic anionic groups forms a complex with the conductive polymer. The second portion of the acidic anionic group is in the form of a salt with a cation selected from inorganic cations, organic cations, and combinations thereof, and the cation concentration is 1 gram solids In the range of 5 × 10 ^{−5 to} 0.2 moles of cation, and the solid content consists essentially of the sum of the conductive polymer and the fully fluorinated acid polymer. Polymer composition.   The conductive polymer according to claim 1, wherein the conductive polymer is formed of at least one monomer selected from the group consisting of thiophenes, selenophenes, tellurophenes, pyrroles, and thienothiophenes. Composition.   The electrically conductive composition according to claim 1, wherein the perfluorinated acid polymer comprises an acidic group selected from the group consisting of sulfonic acid and sulfonamide.   Wherein the perfluorinated acid polymer has a perfluorinated olefin backbone having side groups of perfluorinated alkyl sulfonate groups, perfluorinated ether sulfonate groups, perfluorinated ester sulfonate groups, or perfluorinated ether sulfonimide groups. The conductive composition according to claim 1, comprising:   The conductive polymer composition according to claim 1, wherein the cation is selected from the group consisting of ammonium ion, alkylammonium ion, sodium ion, potassium ion, and combinations thereof. An aqueous dispersion comprising a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups, wherein the first portion of the acidic anionic groups forms a complex with the conductive polymer, The second portion of the acidic anionic group is in the form of a salt with a cation selected from an inorganic cation, an organic cation, and combinations thereof, and the cation concentration is 5 per gram solids. Aqueous dispersion, characterized in that it is in the range of × 10 ^{−5 to} 0.2 mol of cation, and the solid content consists essentially of the sum of the conductive polymer and the fully fluorinated acid polymer. . An electronic device comprising an anode, a buffer layer, a photoactive layer, and a cathode in this order, the buffer layer comprising a conductive polymer and a fully fluorinated acid polymer having acidic anionic groups; The first portion of the acidic anionic group forms a complex with the conductive polymer, and the second portion of the acidic anionic group is selected from an inorganic cation, an organic cation, and combinations thereof. The cation concentration is in the range of 5 × 10 ^{−5 to} 0.2 moles of cation per gram of solid content, and the solid content is the conductivity. An electronic device comprising substantially the sum of a polymer and the perfluorinated acid polymer.

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